π-Donor olefin substituents alter olefin binding to CpFe(CO)₂⁺

A NMR, X-ray, and DFT combined study on the regio-chemistry of nucleophilic addition to platinum(II) coordinated terminal olefins

“…doi:10.1016/j.jorganchem.2008.05.040 increased contribution of the limiting structure [CpFe(CO) 2 (CH 2 -CH@NMe 2 )] + which reduces the bond order between the two carbon atoms [5]. Recent structural and computational studies performed on this iron complex have come to the same conclusion [6]. This interpretation has gained further support in a recent work by Matchett [7].…”

“…Therefore the calculations reproduce well the structural features of these olefin complexes. In particular the calculations reproduce the fact that not all olefins are symmetrically bonded to the metal but a slippage is present in 1b and 1c [6].…”

“…The olefin molecule binds to the platinum(II) centre in an g 2 -fashion and the coordination sphere has the usual square planar arrangement, when the chlorine atom, the two nitrogen atoms Upper and lower entries refer to acetone-d 6 and CDCl 3 solvents, respectively. In the tmeda ligand N-C and C-C distances fall in the normal range.…”

“…Moreover, two solvents were used: CDCl 3 and acetone-d 6 ; the results obtained are listed in Table 2. While using CDCl 3 the formation of the addition reaction products was quantitative, in contrast, in the case of acetone, the addition was accompanied by a side reaction with releasing of free olefin.…”

Reactions of Ruthenium–Aminophosphane Complexes with Diynes: P–N Bond Activation and Formation of Novel Phosphaallyl, Azaallyl, and Aminocarbene Complexes

“…Strong alteration of olefin binding by π-donor substituents has also been observed in [FeCp(CO) 2 (H 2 C=CHNMe 2 )] + where the vinylamine is essentially η 1 -bound [the nonbonded Fe···C separation is 2.823(11) Å]. [15] In turn, the C(24)-N bonds in 3a and 3c exhibit already double bond character being 1.344(2) and 1.359(2) Å, respectively. The bonding situation of the -C=CHNHnPr and -C=CHNC 5 H 10 units might be The structure of 4f also adopts a three-legged piano stool conformation with the η 3 -azaallyl moiety and the P atom as the legs.…”